Metal complexes of iminohydroxamic acids

ABSTRACT

Complexes of the formulae Ia and Ib  
                 
 
     where M=Ti, Zr, Hf, V, Nb, Ta, Cr, Ni, Pd, can be used for the polymerization and copolymerization of olefins, for example in suspension polymerization processes, gas-phase polymerization processes and bulk polymerization processes.

[0001] The present invention relates to complexes of the formulae Ia andIb,

[0002] where the variables are defined as follows:

[0003] Nu is selected from among O, S, N—R⁴, P—R⁴,

[0004] M is selected from among Ti, Zr, Hf, V, Nb, Ta, Cr, Ni, Pd;

[0005] h is an integer from 0 to 4;

[0006] y corresponds to the oxidation state of M minus 1;

[0007] z corresponds to the oxidation state of M minus 2, with theproviso that z is greater than zero;

[0008] X are identical or different and are selected from among halogen,C₁-C₆-alkoxy, acetylacetonate, N(R⁵R⁶), C₁-C₈-alkyl, C₃-C₁₂-cycloalkyl,C₇-C₁₃-aralkyl and C₆-C₁₄-aryl,

[0009] R¹, R⁴ are identical or different and are selected from amonghydrogen,

[0010] C₁-C₁₈-alkyl, substituted or unsubstituted,

[0011] C₂-C₁₈-alkenyl, substituted or unsubstituted, having from

[0012] 1 to 4 isolated or conjugated double bonds;

[0013] C₃-C₁₂-cycloalkyl, substituted or unsubstituted,

[0014] C₇-C₁₃-aralkyl,

[0015] C₆-C₁₄-aryl, unsubstituted or substituted by one or moreidentical or different substituents selected from among

[0016] C₁-C₁₈-alkyl, substituted or unsubstituted,

[0017] C₂-C₁₈-alkenyl, substituted or unsubstituted,

[0018] C₃-C₁₂-cycloalkyl,

[0019] C₇-C₁₃-aralkyl,

[0020] C₆-C₁₄-aryl,

[0021] halogen,

[0022] C₁-C₆-alkoxy, substituted or unsubstituted,

[0023] C₆-C₁₄-aryloxy,

[0024] SiR⁵R⁶R⁷ and O—SiR⁵R⁶R⁷;

[0025] five- to six-membered nitrogen-containing heteroaryl radicals,unsubstituted or substituted by one or more identical or differentsubstituents selected from among

[0026] C₁-C₁₈-alkyl, substituted or unsubstituted,

[0027] C₂-C₁₈-alkenyl, substituted or unsubstituted,

[0028] C₃-C₁₂-cycloalkyl,

[0029] C₇-C₁₃-aralkyl,

[0030] C₆-C₁₄-aryl,

[0031] halogen,

[0032] C₁-C₆-alkoxy,

[0033] C₆-C₁₄-aryloxy,

[0034] SiR⁵R⁶R⁷ and O—SiR⁵R⁶R⁷;

[0035] R² C₆-C₁₄-aryl, unsubstituted or substituted by one or moreidentical or different substituents, or a five- to six-memberednitrogen-containing heteroaryl radical, unsubstituted or substituted byone or more identical or different substituents, where the substituentsare as defined above;

[0036] R³ C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, substituted or unsubstituted,having from one to 4 isolated or conjugated double bonds,C₃-C₁₂-cycloalkyl, substituted or unsubstituted, C₇-C₁₃-aralkyl,C₆-C₁₄-aryl, unsubstituted or substituted by or more identical ordifferent substituents, or a five- to six-membered nitrogen-containingheteroaryl radical, unsubstituted or substituted by one or moreidentical or different substituents, where the substituents are asdefined above;

[0037] where adjacent radicals R¹ to R⁴ may be joined to one another toform a 5- to 12-membered ring which may in turn bear substituentsselected from among C₁-C₈-alkyl, substituted or unsubstituted,C₂-C₈-alkenyl, substituted or unsubstituted, having from one to 4isolated or conjugated double bonds, C₃-C₁₂-cycloalkyl, substituted orunsubstituted, C₇-C₁₃-aralkyl and C₆-C₁₄-aryl;

[0038] L¹ is an uncharged organic or inorganic ligand,

[0039] R⁵ and R⁷ are identical or different and are selected from amonghydrogen, C₁-C₈-alkyl, C₃-C₁₂-cycloalkyl, C₇-C₁₃-aralkyl andC₆-C₁₄-aryl.

[0040] Furthermore, the present invention provides a process for thepolymerization of olefins using complexes of the formulae Ia and Ib.

[0041] Polymers and copolymers of olefins are of great economicimportance because the monomers are readily available in largequantities and because the polymers can be varied within a wide range byvarying the production process or the processing parameters. In theproduction process, the catalyst used is of particular significance.Apart from Ziegler-Natta catalysts, various single-site catalysts are ofincreasing importance, with central atoms which have been examined indetail being Zr, for example in metallocene catalysts (H. -H.Brintzinger et al., Angew. Chem. 1995, 107, 1255) and also Ni or Pd (WO96/23010) and Fe and Co (e.g. WO 98/27124). The complexes of Ni, Pd, Feand Co are also referred to as complexes of late transition metals.

[0042] Metallocene catalysts have disadvantages for industrial use. Themost frequently used metallocenes, i.e. zirconocenes and hafnocenes, aresensitive to hydrolysis. In addition, most metallocenes are sensitive tomany catalyst poisons such as alcohols, ethers or CO, which makes itnecessary for the monomers to be carefully purified.

[0043] While Ni or Pd complexes (WO 96/23010) catalyze the formation ofthe highly branched, commercially less interesting polymers, the use ofFe or Co complexes leads to formation of highly linear polyethylenehaving a very low comonomer content.

[0044] EP-A 0 874 005 discloses further polymerization-active complexes.These are preferably titanium complexes with salicylaldimine ligands.They too bear phenyl substituents or substituted phenyl substituents onthe aldimine nitrogen (pages 18-23), or else the aldimine nitrogen ispart of a 6-membered ring (pages 31-32). However, they generally producelow molecular weight polyethylenes which are not very suitable asmaterials. Furthermore, in all the ligands disclosed in EP-A 0 874 005,the oxygen atom is part of a phenolic system, which restricts the choiceof readily available starting materials.

[0045] As G. J. P. Britovsek et al. demonstrate in Angew. Chem. 1999,111, 448 and Angew. Chem. Int. Ed. Engl. 1999, 38, 428, the search forvery versatile polymerization-active complexes continues to be importantbecause of the great commercial importance of polyolefins. Particularattention has been paid to complexes of the early transition metals withbidentate ligands, for example complexes of the formula A,

[0046] which have been studied by X. Bei et al. in Organometallics 1997,16, 3282. However, the activities of the complexes in which M=Ti or Zrand in the polymerization of ethylene were too low for the complexes tobe of commercial interest. T. Tsukahara et al. in Organometallics 1997,16, 3303 and I. Kim et al. in Organometallics 1997, 16, 3314 haveexamined β-hydroxypyridyl complexes of the formula B

[0047] and their activity in the polymerization of ethylene. If, forexample, R is CH₃ or CF₃ and X is benzyl or neopentyl, thepolymerization activity displayed toward ethylene was extremely low ornonexistent when the complex was activated withtrispentafluorophenylborane. In contrast, when R waspara-tert-butylphenyl and X was benzyl, some activity was observed, butthis was too low for commercial purposes.

[0048] In Aust. J. Chem. 1976, 29, 357, L. H. Biggs et al. reportcomplexes of the formula C

[0049] and examine them for activity against tumors. Complexes of theformula C are polymerization-inactive.

[0050] It is an object of the invention

[0051] to provide novel complexes which are suitable for thepolymerization of olefins to give high molecular weight polymers;

[0052] to provide a process for preparing the complexes of the presentinvention;

[0053] to provide a process for the polymerization or copolymerizationof olefins using the complexes of the present invention;

[0054] to provide supported catalysts for the polymerization of olefinsand also a process for preparing the supported catalysts of the presentinvention using the complexes of the present invention;

[0055] to polymerize and copolymerize olefins by means of the supportedcatalysts of the present invention.

[0056] We have found that this object is achieved by complexes whichhave the structures of the formulae Ia and Ib as defined at the outset.

[0057] In formula I, the variables are defined as follows:

[0058] Nu is selected from among O, S, N—R⁴ and P—R⁴, with oxygen andN—R⁴ being preferred;

[0059] M is selected from among Ti, Zr, Hf, V, Nb, Ta, Cr, Ni and Pd inthe oxidation states from +2 to +5; preference is given to Ti or Zr inthe oxidation state +4 or Ni in the oxidation state +2 and particularpreference is given to Zr or Ni;

[0060] h is an integer from 0 to 4; in the case of M=Ti or Zr or Hf, his preferably 0; in the case of M=Ni or Pd, h is preferably not equal to0 and is particularly preferably 1 or 2;

[0061] y corresponds to the oxidation state of M minus 1,

[0062] z corresponds to the oxidation state of M minus 2, where M can bea metal in the highest oxidation state but does not have to be and z isgreater than zero;

[0063] X are identical or different and are selected from among

[0064] halogen, such as fluorine, chlorine, bromine and iodine;preference is given to chlorine or bromine and particular preference isgiven to chlorine;

[0065] C₁-C₆-alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy,n-hexoxy and isohexoxy, particularly preferably methoxy, ethoxy,n-propoxy and n-butoxy;

[0066] acetylacetonate,

[0067] N(R⁵R⁶), where R⁵ and R⁶ are as defined below, particularlypreferably N(CH₃)₂, N(CH₃) (C₆H₅) or N(CH₂)₄

[0068] C₁-C₈-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,n-heptyl, isoheptyl and n-octyl; preferably C₁-C₆-alkyl such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,n-hexyl, isohexyl, sec-hexyl, particularly preferably C₁-C₄-alkyl suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl andtert-butyl;

[0069] C₃-C₁₂-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0070] C₇-C₁₃-aralkyl, preferably C₇-C₁₂-phenylalkyl such as benzyl,1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, neophyl (1-methyl-1-phenylethyl), 1-phenylbutyl,2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferablybenzyl; and

[0071] C₆-C₁₄-aryl, for example phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl,1-naphthyl and 2-naphthyl, particularly preferably phenyl.

[0072] X is preferably halogen. When M is selected from among Ni and Pd,

[0073] X is very particularly preferably C₁-C₄-alkyl or C₆-C₁₄-aryl.

[0074] R¹ and R⁴ are identical or different and are selected from among

[0075] hydrogen,

[0076] C₁-C₁₈-alkyl groups such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-decyl, n-dodecyl andn-octadecyl; preferably C₁-C₁₂-alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,isohexyl, sec-hexyl and n-decyl, particularly preferably C₁-C₄-alkylsuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyland tert-butyl;

[0077] examples of substituted C₁-C₁₈-alkyl groups are: monohalogenatedor polyhalogenated C₁-C₈-alkyl groups such as fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl,pentafluoroethyl, perfluoropropyl and perfluorobutyl; particularpreference is given to fluoromethyl, difluoromethyl, trifluoromethyl andperfluorobutyl;

[0078] C₂-C₁₈-alkenyl having from one to 4 isolated or conjugated doublebonds, for example vinyl, 1-allyl, 3-allyl, ω-butenyl, ω-pentenyl,ω-hexenyl, 1-cis-buta-1,3-dienyl and 1-cis-hexa-1,5-dienyl;

[0079] examples of substituted C₂-C₁₈-alkenyl groups are: isopropenyl,1-isoprenyl, α-styryl, β-styryl, 1-cis-1,2-phenylethenyl and1-trans-1,2-phenylethenyl;

[0080] C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0081] examples of substituted cycloalkyl groups are:2-methylcyclopentyl, 3-methylcyclopentyl, cis-2,4-dimethylcyclopentyl,trans-2,4-dimethylcyclopentyl, cis-2,5-dimethylcyclopentyl,trans-2,5-dimethylcyclopentyl, 2,2,5,5-tetramethylcyclopentyl,2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,cis-2,6-dimethylcyclohexyl, trans-2,6-dimethylcyclohexyl,cis-2,6-diisopropylcyclohexyl, trans-2,6-diisopropylcyclohexyl,2,2,6,6-tetramethylcyclohexyl, 2-methoxycyclopentyl,2-methoxycyclohexyl, 3-methoxycyclopentyl, 3-methoxycyclohexyl,2-chlorocyclopentyl, 3-chlorocyclopentyl, 2,4-dichlorocyclopentyl,2,2,4,4-tetrachlorocyclopentyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl,4-chlorocyclohexyl, 2,5-dichlorocyclohexyl,2,2,6,6-tetrachlorocyclohexyl, 2-thiomethylcyclopentyl,2-thiomethylcyclohexyl, 3-thiomethylcyclopentyl, 3-thiomethylcyclohexyland further derivatives;

[0082] C₇-C₁₃-aralkyl, preferably C₇-C₁₂-phenylalkyl such as benzyl,1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, neophyl (1-methyl-1-phenylethyl), 1-phenylbutyl,2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferablybenzyl;

[0083] C₆-C₁₄-aryl, for example phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl und 9-phenanthryl, preferably phenyl,1-naphthyl and 2-naphthyl, particularly preferably phenyl;

[0084] C₆-C₁₄-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, substituted by one or more identical ordifferent substituents selected from among

[0085] C₁-C₁₈-alkyl groups such as methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl n-octyl, n-decyl, n-dodecyl andn-octadecyl; preferably C₁-C₁₂-alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,isohexyl, sec-hexyl or n-decyl, particularly preferably C₁-C₄-alkyl suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl andtert-butyl;

[0086] examples of substituted C₁-C₈-alkyl groups are: monohalogenatedor polyhalogenated C₁-C₈-alkyl groups such as fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl,pentafluoroethyl, perfluoropropyl and perfluorobutyl; particularpreference is given to fluoromethyl, difluoromethyl, trifluoromethyl andperfluorobutyl;

[0087] C₂-C₁₈-alkenyl having from one to 4 isolated or conjugated doublebonds, for example vinyl, 1-allyl, 3-allyl, ω-butenyl, ω-pentenyl,ω-hexenyl, 1-cis-buta-1,3-dienyl and 1-cis-hexa-1,5-dienyl.

[0088] examples of substituted C₂-C₁₈-alkenyl groups are: isopropenyl,1-isoprenyl, α-styryl, β-styryl, 1-cis-1,2-phenylethenyl and1-trans-1,2-phenylethenyl.

[0089] C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0090] C₇-C₁₃-aralkyl, preferably C₇-C₁₂-phenylalkyl such as benzyl,1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, neophyl (1-methyl-1-phenylethyl), 1-phenylbutyl,2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferablybenzyl;

[0091] C₆-C₁₄-aryl, for example phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl,1-naphthyl and 2-naphthyl, particularly preferably phenyl;

[0092] halogen, for example fluorine, chlorine, bromine and iodine,particularly preferably fluorine and chlorine;

[0093] C₁-C₆-alkoxy groups such as methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy,isopentoxy, n-hexoxy and isohexoxy, particularly preferably methoxy,ethoxy, n-propoxy and n-butoxy;

[0094] C₆-C₁₄-aryloxy groups such as phenoxy, ortho-cresyloxy,meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy and9-anthryloxy;

[0095] silyl groups SiR⁵R⁶R⁷, where R⁵ to R⁷ are selected independentlyfrom among hydrogen, C₁-C₈-alkyl groups, the benzyl radical andC₆-C₁₄-aryl groups; preference is given to the trimethylsilyl,triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl,tribenzylsilyl, triphenylsilyl and tri-para-xylylsilyl groups;particular preference is given to the trimethylsilyl group and thetert-butyldimethylsilyl group;

[0096] silyloxy groups OSiR⁵R⁶R⁷, where R⁵ to R⁷ are selectedindependently from among hydrogen, C₁-C₈-alkyl groups, the benzylradical and C₆-C₁₄-aryl groups; preference is given to thetrimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy,diethylisopropylsilyloxy, dimethylthexylsilyloxy,tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,tribenzylsilyloxy, triphenylsilyloxy and tri-para-xylylsilyloxy groups;particular preference is given to the trimethylsilyloxy group and thetert-butyldimethylsilyloxy group;

[0097] five- and six-membered nitrogen-containing heteroaryl radicalssuch as N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, N-imidazolyl,2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl,2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl;

[0098] five- and six-membered nitrogen-containing heteroaryl radicalssuch as N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, N-imidazolyl,2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl, 1,2,4-triazol-4-yl,2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl,2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl,substituted by one or more identical or different substituents selectedfrom among

[0099] C₁-C₁₈-alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl,sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-decyl, n-dodecyl andn-octadecyl; preferably C₁-C₁₂-alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,isohexyl, sec-hexyl and n-decyl, particularly preferably C₁-C₄-alkylsuch as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyland tert-butyl;

[0100] examples of substituted C₁-C₈-alkyl groups are: monohalogenatedor polyhalogenated C₁-C₈-alkyl groups such as fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl,pentafluoroethyl, perfluoropropyl and perfluorobutyl; particularpreference is given to fluoromethyl, difluoromethyl, trifluoromethyl andperfluorobutyl;

[0101] C₂-C₁₈-alkenyl having from one to 4 isolated or conjugated doublebonds, for example vinyl, 1-allyl, 3-allyl, ω-butenyl, ω-pentenyl,ω-hexenyl, 1-cis-buta-1,3-dienyl and 1-cis-hexa-1,5-dienyl.

[0102] examples of substituted C₂-C₁₈-alkenyl groups are: isopropenyl,1-isoprenyl, α-styryl, β-styryl, 1-cis-1,2-phenylethenyl and1-trans-1,2-phenylethenyl.

[0103] C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0104] C₇-C₁₃-aralkyl, preferably C₇-C₁₂-phenylalkyl such as benzyl,1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, neophyl (1-methyl-1-phenylethyl), 1-phenylbutyl,2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferablybenzyl;

[0105] C₆-C₁₄-aryl, for example phenyl, 1-naphthyl, 2-naphthyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl,1-naphthyl and 2-naphthyl, particularly preferably phenyl;

[0106] halogen, for example fluorine, chlorine, bromine and iodine,particularly preferably fluorine and chlorine;

[0107] C₁-C₆-alkoxy groups such as methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy,isopentoxy, n-hexoxy and isohexoxy, particularly preferably methoxy,ethoxy, n-propoxy and n-butoxy;

[0108] C₆-C₁₄-aryloxy groups such as phenoxy, ortho-cresyloxy,meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy and9-anthryloxy;

[0109] silyl groups SiR⁵R⁶R⁷, where R⁵ to R⁷ are selected independentlyfrom among hydrogen, C₁-C₈-alkyl groups, the benzyl radical andC₆-C₁₄-aryl groups; preference is given to the trimethylsilyl,triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,dimethylthexylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl,tribenzylsilyl, triphenylsilyl and tri-para-xylylsilyl groups;particular preference is given to the trimethylsilyl group and thetert-butyldimethylsilyl group;

[0110] silyloxy groups OSiR⁵R⁶R⁷, where R⁵ to R⁷ are selectedindependently from among hydrogen, C₁-C₈-alkyl groups, the benzylradical and C₆-C₁₄-aryl groups; preference is given to thetrimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy,diethylisopropylsilyloxy, dimethylthexylsilyloxy,tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,tribenzylsilyloxy, triphenylsilyloxy and tri-para-xylylsilyloxy groups;particular preference is given to the trimethylsilyloxy group and thetert-butyldimethylsilyloxy group;

[0111] In a particularly preferred embodiment, R¹ or R⁴ is not hydrogen.

[0112] R² is C₆-C₁₄-aryl, unsubstituted or substituted by one or moreidentical or different substituents, or a five- or six-memberednitrogen-containing heteroaryl radical, unsubstituted or substituted byone or more identical or different substituents, where the substituentsare as defined above.

[0113] R³ and R⁸ are identical or different and are selected from amongC₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, substituted or unsubstituted, having fromone to 4 isolated or conjugated double bonds, C₃-C₁₂-cycloalkyl,substituted or unsubstituted, C₇-C₁₃-aralkyl, C₆-C₁₄-aryl, unsubstitutedor substituted by one or more identical or different substituents, andfive- to six-membered nitrogen-containing heteroaryl radicals,unsubstituted or substituted by one or more identical or differentsubstituents, where the substituents are as defined above.

[0114] In a particularly preferred embodiment, R¹ is selected from among2,6-diisopropylphenyl, 2,6-dimethylphenyl and ortho-biphenyl.

[0115] In a particularly preferred embodiment, R² is phenyl.

[0116] L¹ is selected from among uncharged inorganic and organicligands, for example phosphines of the formula (R⁸)_(x)PH_(3−x) andamines of the formula (R⁸)_(x)NH_(3−x), where x is an integer from 0 to3. Also suitable are ethers (R⁸)₂O such as dialkyl ethers, e.g. diethylether, or cyclic ethers, e.g. tetrahydrofuran, H₂O, alkohols (R⁸)OH suchas methanol or ethanol, pyridine, pyridine derivatives of the formulaC₅H_(5−x)(R⁸)_(x)N, for example 2-picoline, 3-picoline, 4-picoline,2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine or 3,5-lutidine,CO, C₁-C₁₂-alkyl nitriles or C₆-C₁₄-aryl nitriles, e.g. acetonitrile,propionitrile, butyronitrile or benzonitrile. It is also possible to usesingly or multiply ethylenically unsaturated double bond systems asligand, e.g. ethenyl, propenyl, cis-2-butenyl, trans-2-butenyl,cyclohexenyl or norbornenyl.

[0117] In a particular embodiment, adjacent radicals R¹ to R⁴ in thecomplexes of the formulae Ia and Ib may be joined to one another to forma 5- to 12-membered ring. For example, R³ and R⁴ may together be:—(CH₂)₃— (trimethylene), —(CH₂)₄— (tetramethylene), —(CH₂)₅—(pentamethylene), —(CH₂)₆— (hexamethylene), —CH₂—CH═CH—,—CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—, —O—CH₂—O—, —O—CHMe—O—, —O—CH—(C₆H₅)—O—,—O—CH₂—CH₂—O—, —O—CMe₂—O—, —NMe—CH₂—CH₂—NMe—, —NMe—CH₂—NMe— or—O—SiMe₂—O— where Me=CH₃. In a further embodiment of the presentinvention, R¹ and R⁶ are joined to one another to form a 5- to12-membered ring.

[0118] In another preferred embodiment, L¹ and X are joined to oneanother; for example L¹ and X can together form an allyl anion or a2-methylallyl anion.

[0119] The complexes required for the process of the present inventioncan be synthesized readily.

[0120] The synthesis of the novel complexes of the formulae Ia and Ibgenerally starts out from a protonated ligand of the formula II,

[0121] where the variables are as defined above.

[0122] The protonated ligands of the formula II are firstly deprotonatedby means of a base and subsequently reacted with metal compounds of theformula MX_(y+1).

[0123] As base, it is possible to use the metal alkyls customary inorganometallic chemistry, for example methyllithium, ethyllithium,n-butyllithium, sec-butyllithium, tert-butyllithium or hexyllithium,also Grignard compounds such as ethylmagnesium bromide, also lithiumamide, sodium amide, potassium amide, potassium hydride or lithiumdiisopropylamide (“LDA”). Solvents which have been found to be usefulare toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene ormixtures thereof, also noncyclic or cyclic ethers such as1,2-dimethoxyethane, tetrahydrofuran or diethyl ether.

[0124] This deprotonation is generally complete after a few hours; anappropriate reaction time is from 2 to 10 hours, preferably from 3 to 5hours. The temperature conditions are generally not critical; carryingout the deprotonation at from −90° C. to −20° C. is preferred.

[0125] If a metal compound MX_(y+1) in which X is C₁-C₈-alkyl,C₃-C₁₂-cycloalkyl, C₇-C₁₃-aralkyl or C₆-C₁₄-aryl is chosen, the use of abase can generally be omitted.

[0126] The deprotonated ligand and the metal compound of the formulaMX_(y+1) are subsequently reacted with one another.

[0127] Here, MX_(y+1) can optionally be stabilized by uncharged ligands.Possible uncharged ligands are the customary ligands of coordinationchemistry, for example cyclic and noncyclic ethers, amines, diamines,nitriles, isonitriles or phosphines. Particular preference is given todiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,tetramethylethylenediamine, acetonitrile or triphenylphosphine.

[0128] The conditions for the reaction are not critical per se; it isusual to mix the deprotonated ligand II and MX_(y+1) with one another ina suitable solvent such as benzene, toluene, ethylbenzene, ortho-xylene,meta-xylene or para-xylene, chlorobenzene, cyclohexane, methylenechloride or a mixture thereof. A suitable temperature range is from−100° C. to +150° C., preferably from −78° C. to +100° C. The reactiontemperature should not have been below the melting point of the solvent;temperatures above tbe boiling point of the respective solvent can beachieved in an autoclave. It is important that the reaction is carriedout with exclusion of oxygen and moisture.

[0129] The molar ratio of ligand to M may be in the range from 5:1 to1:5. However, since the ligands of the formula II are the reactantswhich are costlier/more difficult to obtain, preference is given tomolar ratios of ligand: M in the range from 1:1 to 1:3, particularlypreferably stoichiometric amounts.

[0130] If, however, compounds of the formula Ib are to be obtained,molar ratios of ligand: M of from 2:1 to 4:1 are preferred.

[0131] The novel complexes of the formulae Ia and Ib can be purified bythe methods customary in organometallic chemistry, with crystallizationand precipitation being particularly preferred; filtration throughfilter aids such as Celite® is also useful.

[0132] The preparation of the protonated ligands of the formula II isknown per se and can be carried out particularly well by reacting anamide of the formula III,

[0133] which bears an acidic α-H atom on the nitrogen, with ahalogenating agent such as SO₂Cl₂, PCl₃ or POCl₃ and subsequentlyreacting the product with a nucleophilic compound of the formula IV,

[0134] where the variables in the compounds III and IV are as definedabove, in the presence of a base. By-products formed can be separatedoff by customary purification methods.

[0135] As base, preference is given to using tertiary amines such astriethylamine, diisopropylethylamine or pyridine. Solvents which havebeen found to be suitable are alcohols or chlorinated hydrocarbons, forexample methylene chloride or chloroform, or mixtures thereof; it isalso possible to use noncyclic or cyclic ethers such as1,2-dimethoxyethane, tetrahydrofuran or diethyl ether.

[0136] This reaction is generally complete after a period of from a fewminutes to a few hours; an appropriate reaction time is from 30 minutesto 10 hours, preferably from 1 to 5 hours. The temperature conditionsare generally not critical; preference is given to carrying out thereaction at from −90° C. to +30° C., in exceptional cases up to 50° C.

[0137] The reaction is preferably carried out with exclusion of oxygenand moisture.

[0138] The molar ratio of III to IV may be in the range from 5:1 to 1:5;preference is given to molar ratios III:IV in the range from 3:1 to 1:3,and particular preference is given to stoichiometric amounts.

[0139] Acid amides of the formula III can be obtained by generally knownamidation reactions, for example by reaction of carboxylic acids ortheir esters, carboxylic acid chlorides or carboxylic anhydrides withamines, in the presence or absence of a coupling reagent or a base.

[0140] It has been found that the novel complexes of the formulae Ia andIb are suitable for the polymerization of olefins. They polymerize andcopolymerize ethylene and polypropylene particularly well to give highmolecular weight polymers. Complexes of the formula Ib are chiral: theycan give isotactic polypropylene in the polymerization.

[0141] For the novel complexes of the formulae Ia and Ib to becatalytically active, they have to be activated. Suitable activators forcomplexes in which M is selected from among Ti, Zr, Hf, V, Nb, Ta and Crare selected aluminum or boron compounds bearing electron-withdrawingradicals (e.g. trispentafluorophenylborane,trispentafluorophenylaluminum, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bisperfluoromethylphenyl) borate, tri-n-butylammoniumtetrakis (3,5-bisperfluoromethylphenyl)borate and trityliumtetrakis(pentafluorophenyl)borate. Preference is given todimethylanilinium tetrakis(pentafluorophenyl)borate, trityliumtetrakis(pentafluorophenyl)borate and trispentafluorophenylborane.

[0142] If boron or aluminum compounds are used as activators for thenovel compounds of the formulae Ia and Ib, they are generally used in amolar ratio of from 1:10 to 10:1, based on M; preferably from 1:2 to 5:1and particularly preferably in stoichiometric amounts.

[0143] Aluminoxanes form another useful class of activators. Thestructure of the aluminoxanes is not known precisely. They are productswhich are obtained by careful partial hydrolysis of aluminum alkyls (cf.DE-A 30 07 725). These products are not in the form of pure singlecompounds, but are mixtures of open-chain and cyclic structures of thetypes Va and Vb. These mixtures are presumably in dynamic equilibrium.

[0144] In the formulae Va and Vb, the radicals R^(m) are each,independently of one another,

[0145] C₁-C₁₂-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl or n-dodecyl; preferablyC₁-C₆-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl,particularly preferably methyl;

[0146] C₃-C₁₂-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl or cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0147] C₇-C₂₀-aralkyl, preferably C₇-C₁₂-phenylalkyl such as benzyl,1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl or4-phenylbutyl, particularly preferably benzyl, or

[0148] C₆-C₁₄-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl or 9-phenanthryl, preferably phenyl, 1-naphthyl or2-naphthyl, particularly preferably phenyl; and

[0149] n is an integer from 0 to 40, preferably from 1 to 25 andparticularly preferably from 2 to 22.

[0150] Cage-like structures for aluminoxanes are also discussed in theliterature (Y. Koide, S. G. Bott, A. R. Barron Organometallics 1996, 15,2213-26; A. R. Barron Macromol. Symp. 1995, 97, 15-25). Regardless ofthe actual structure of the aluminoxanes, they are suitable asactivators for the novel metal complexes of the formulae Ia and Ib.

[0151] Mixtures of various aluminoxanes are particularly preferredactivators in cases in which the polymerization is carried out insolution in a paraffin, for example n-heptane or isododecane. Aparticularly prefered mixture is CoMAO which is commercially availablefrom Witco GmbH and has the formula [(CH₃)_(0.9)(iso-C₄H₉)_(0.1)AlO]_(n).

[0152] To activate the complexes of the formulae Ia and Ib by means ofaluminoxanes, it is generally necessary to employ an excess ofaluminoxane, based on M. Useful molar ratios M:Al are in the range from1:10 to 1:10 000, preferably from 1:50 to 1:1000 and particularlypreferably from 1:100 to 1:500.

[0153] The chosen complex of the formula Ia or Ib and the activatortogether form a catalyst system.

[0154] The activity of the catalyst system according to the presentinvention can be increased by addition of further aluminum alkyl of theformula Al(R^(m))₃ or aluminoxanes; aluminum alkyls of the formulaAl(R^(m))₃ or aluminoxanes can also act as molar mass regulators. Afurther effective molar mass regulator is hydrogen. The molar mass canbe regulated particularly well by means of the reaction temperature andthe pressure. If the use of a boron compound as described above isdesired, the addition of an aluminum alkyl of the formula Al(R^(m))₃ isparticularly preferred.

[0155] When M is Ni or Pd, preference is given to using olefin complexesof rhodium or nickel as activator.

[0156] Preferred nickel(olefin)_(y) complexes with y=1, 2, 3 or 4 whichare commercially available, e.g. from Aldrich, are Ni(C₂H₄)₃,Ni(1,5-cyclooctadiene)₂ “Ni(COD)₂”, Ni(1,6-cyclodecadiene)₂ andNi(1,5,9-all-trans-cyclododecatriene)₂. Particular preference is givento Ni(COD)₂.

[0157] Particularly useful olefin complexes are mixedethylene/1,3-dicarbonyl complexes of rhodium, for example(ethylene)rhodium acetylacetonate Rh(acac) (CH₂═CH₂)₂, (ethylene)rhodiumbenzoylacetonate Rh(C₆H₅—CO—CH—CO—CH₃) (CH₂═CH₂)₂ orRh(C₆H₅—CO—CH—CO—C₆H₅) (CH₂═CH₂)₂. The most useful complex is Rh(acac)(CH₂═CH₂)₂. This compound can be synthesized by the method described byR. Cramer in Inorg. Synth. 1974, 15, 14.

[0158] Some complexes of the formula Ia can be activated by means ofethylene. The ease of the activation reaction depends critically on thenature of the ligand L¹.

[0159] Pressure and temperature conditions during the polymerization canbe chosen within wide limits. A pressure in the range from 0.5 bar to4000 bar has been found to be useful; preference is given to from 10 to75 bar or high-pressure conditions of from 500 to 2500 bar.

[0160] A suitable temperature range has been found to be from 0 to 120°C., preferably from 40 to 100° C. and particularly preferably from 50 to85° C.

[0161] As monomers, mention may be made of the following olefines:ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-deceneand 1-undecene, with propylene and ethylene being preferred and ethylenebeing particularly preferred. Styrene can also be used as monomer.

[0162] Suitable comonomers are α-olefins, for example from 0.1 to 20 mol% of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene or 1-undecene. However, isobutene and styrene are also suitablecomonomers, also internal olefins such as cyclopentene, cyclohexene,norbornene and norbornadiene.

[0163] As solvents, toluene, ortho-xylene, meta-xylene, para-xylene,ethylbenzene and mixtures thereof have been found to be useful.Supercritical ethylene can also be employed under high-pressureconditions.

[0164] The catalyst systems of the present invention polymerize olefinsto give polyolefins having a very high molecular weight.

[0165] The catalyst systems of the present invention can be regulated bymeans of hydrogen in the polymerization, i.e. the molecular weight ofthe polymers obtainable by means of the catalyst system of the presentinvention can be reduced by addition of hydrogen. If sufficient hydrogenis added, polyolefin waxes are obtained. The preferred concentration ofhydrogen also depends on the type of polymerization plant used.

[0166] For the catalyst systems of the present invention to be able tobe used in modern polymerization processes such as suspension processes,bulk polymerization processes or gas-phase processes, it is necessaryfor them to be immobilized on a solid support. Otherwise, morphologyproblems with the polymer (lumps, deposits on walls, blockages in linesor heat exchangers) can occur and force shutdown of the plant. Such animmobilized catalyst system is referred to as catalyst.

[0167] The catalyst systems of the present invention can be deposited onsolid support materials. Possible support materials are, for example,porous oxides of metals of groups 2 to 14 or mixtures thereof, alsosheet silicates and zeolites. Preferred examples of metal oxides ofgroups 2 to 14 are SiO₂, B₂O₃, Al₂O₃, MgO, CaO and ZnO. Preferred sheetsilicates are montmorillonites or bentonites; as zeolite, preference isgiven to using MCM-41.

[0168] Particularly preferred support materials are spherical silicagels and aluminosilicate gels of the formula SiO₂.a Al₂O₃, where a isgenerally in the range from 0 to 2, preferably from 0 to 0.5. Suchsilica gels are commercially available, e.g. silica gel SG 332, Sylopol®948 or 952 or S 2101 from W. R. Grace or ES 70X from Crosfield.

[0169] Suitable particle sizes of the support material are mean particlediameters in the range from 1 to 300 μm, preferably from 20 to 80 μm, asdetemined by known methods such as sieving. The pore volume of thesupport is from 1.0 to 3.0 ml/g, preferably from 1.6 to 2.2 ml/g andparticularly preferably from 1.7 to 1.9 ml/g. The BET surface area isfrom 200 to 750 m²/g, preferably from 250 to 400 m²/g.

[0170] To remove impurities, in particular moisture, adhering to thesupport material, the support materials can be baked before applicationof the active catalyst complex. Suitable temperatures for this are inthe range from 45 to 1000° C. Temperatures of from 100 to 750° C. areparticularly suitable for silica gels and other metal oxides. Thisbaking can be carried out over a period of from 0.5 to 24 hours, withtimes of from 1 to 12 hours being preferred. The pressure conditions aredependent on the process chosen; baking can be carried out in a fixedbed, a stirred vessel or else in a fluidized bed. Baking can be carriedout at atmospheric pressure, but reduced pressures of from 0.1 to 500mbar are advantageous. A range from 1 to 100 mbar is particularlyadvantageous and a range from 2 to 20 mbar is very particularlyadvantageous. On the other hand, fluidized-bed processes areadvantageously carried out at a slightly superatmospheric pressure inthe range from 1.01 bar to 5 bar, preferably from 1.1 to 1.5 bar.

[0171] Chemical pretreatment of the support material with an alkylcompound such as an aluminum alkyl, a lithium alkyl or an aluminoxane islikewise possible.

[0172] In a suspension polymerization, use is made of suspension mediain which the desired polymer is insoluble or only slightly soluble,because otherwise deposits of product are obtained in plant componentsin which the product is separated from the suspension medium and thismakes repeated shutdowns and cleaning operations necessary. Suitablesuspension media are saturated hydrocarbons such as propane, n-butane,isobutane, n-pentane, isopentane, n-hexane, isohexane and cyclohexane,with isobutane being preferred.

[0173] Pressure and temperature conditions during the polymerization canbe chosen within wide limits. A pressure in the range from 0.5 bar to150 bar has been found to be useful; preference is given to from 10 to75 bar. A suitable temperature range has been found to be from 0 to 120°C., preferably from 40 to 100° C.

[0174] As monomers, mention may be made of the following olefins:ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-deceneand 1-undecene. Styrene can also be used as monomer.

[0175] Suitable comonomers are α-olefins, for example from 0.1 to 20 mol% of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene or 1-undecene. However, isobutene and styrene are also suitablecomonomers, also internal olefins such as cyclopentene, cyclohexene,norbornene and norbornadiene.

[0176] The catalysts of the present invention have, overall, anadvantageous use profile in process engineering terms.

[0177] Furthermore, the catalysts of the present invention have beenfound to be able to be regulated by means of hydrogen, i.e. themolecular weight of the polymers obtainable by means of the catalysts ofthe present invention can be reduced by addition of hydrogen. Waxes areobtained when sufficient hydrogen is added, with the hydrogenconcentration required also depending on the type of polymerizationplant used. Addition of hydrogen generally increases the activity of thecatalysts of the present invention.

[0178] The catalysts of the present invention can also be used togetherwith one or more other polymerization catalysts known per se. Thus, forexample, they can be used together with

[0179] Ziegler-Natta catalysts,

[0180] supported metallocene catalysts containing transition metals ofgroups 4 to 6 of the Periodic Table of the Elements,

[0181] catalysts based on late transition metals (WO 96/23010),

[0182] Fe or Co complexes with pyridyldiimine ligands, as are disclosedin WO 98/27124,

[0183] or chromium oxide catalyts of the Phillips type.

[0184] If a number of catalysts are used, it is possible to mix variouscatalysts with one another and to introduce them together into thepolymerization or to use cosupported complexes on a common support orelse to meter various catalyts separately into the polymerization vesselat the same point or at different points.

[0185] Furthermore, it has been found that the novel complexes of theformulae Ia and Ib, in particular those in which M=Ni, are particularlyuseful for the polymerization or copolymerization of 1-olefins,preferably ethylene, in emulsion polymerization processes.

[0186] Apart from other 1-olefins as comonomers, for example propene,1-butene, 1-hexene, 1-octene or 1-decene, or vinylaromatic compoundssuch as styrene, it is also possible for polar comonomers to beincorporated by means of the catalyst system of the present invention,with from 0.1 to 50 mol % of comonomers being able to be used.Preference is given to

[0187] acrylates such as acrylic acid, methyl acrylate, ethyl acrylate,2-ethylhexyl acrylate, n-butyl acrylate or tert-butyl acrylate;

[0188] methacrylic acid, methyl methacrylate, ethyl methacrylate,n-butyl methacrylate or tert-butyl methacrylate;

[0189] vinylaromatic compounds such as styrene;

[0190] vinyl carboxylates, particularly preferably vinyl acetate,

[0191] unsaturated dicarboxylic acids, particularly preferably maleicacid,

[0192] unsaturated dicarboxylic acid derivatives, particularlypreferably maleic anhydride and alkylimides of maleic acid, e.g. themethylimide of maleic acid.

[0193] It is also possible to prepare terpolymers comprising at least 2of the abovementioned monomers together with ethylene.

[0194] The emulsion polymerization of the 1-olefins using the metalcomplexes of the formula I as provided by the present invention can becarried out in a manner known per se.

[0195] The order of addition of the reagents in the polymerization isnot critical. Thus, the solvent can firstly be pressurized with gaseousmonomer or liquid monomer can be metered in, followed by addition of thecatalyst system. However, it is also possible for the solution of thecatalyst system firstly to be diluted with further solvent and themonomer to be added subsequently.

[0196] The actual polymerization is usually carried out at a minimumpressure of 1 bar; below this pressure, the polymerization rate is toolow. Preference is given to 2 bar and particular preference is given toa minimum pressure of 10 bar.

[0197] A practical maximum pressure is 4000 bar; at higher pressures,the demands made of the material of which the polymerization reactor isconstructed are very high and the process becomes uneconomical.Preference is given to 100 bar and particular preference is given to 50bar.

[0198] The polymerization temperature can be varied within a wide range.A practical minimum temperature is 10° C., since the polymerization ratedecreases at low temperatures. Preference is given to a minimumtemperature of 40° C., particularly preferably 65° C. The maximumpractical temperature is 350° C. and preference is given to a maximumtemperature of 150° C., particularly preferably 100° C.

[0199] Before the polymerization, the complex of the formula Ia or Ib isdissolved in an organic solvent or in water. The solution is stirred orshaken for a number of minutes to ensure that it is clear. The stirringtime can, depending on the solubility of the complex concerned, be from1 to 100 minutes.

[0200] At the same time, any activator necessary is dissolved in asecond portion of the same solvent or else in acetone.

[0201] Suitable organic solvents are aromatic solvents such as benzene,toluene, ethylbenzene, ortho-xylene, meta-xylene and para-xylene andmixtures thereof. Also suitable are cyclic ethers such astetrahydrofuran and dioxane or noncyclic ethers such as diethyl ether,di-n-butyl ether, diisopropyl ether or 1,2-dimethoxyethane. It is alsopossible to use ketones such as acetone, methyl ethyl ketone ordiisobutyl ketone, likewise amides such as dimethylformamide ordimethylacetamide. Mixtures of these solvents with one another and alsomixtures of these solvents with water or alcohols such as methanol orethanol are also possible.

[0202] Preference is given to acetone and water and mixtures of acetoneand water, with any mixing ratio being possible. The amount of solventis likewise not critical, but it has to be ensured that the complex andthe activator can dissolve completely, otherwise a reduced activity hasto be expected. The dissolution can, if appropriate, be accelerated byultrasonic treatment.

[0203] If an emulsifier is to be added, it can be dissolved in a thirdportion of the solvent or else together with the complex. The amount ofany such emulsifier is selected so that the mass ratio of monomer toemulsifier is greater than 1, preferably greater than 10 andparticularly preferably greater than 20. The less emulsifier which hasto be used, the better. The activity of the polymerization issignificantly increased if an emulsifier is added. This emulsifier canbe nonionic or ionic in nature.

[0204] Nonionic emulsifiers which can be used are, for example,ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols (EOcontent: 3-50, alkyl radical: C₄-C₁₂) and ethoxylated fatty alcohols (EOcontent: 3-80; alkyl radical: C₈-C₃₆). Examples are the Lutensol® gradesfrom BASF AG or the Triton® grades from Union Carbide.

[0205] Customary anionic emulsifiers are, for example, alkali metal andammonium salts of alkyl sulfates (alkyl radical: C₈ to C₁₂), of sulfuricmonoesters of ethoxylated alkanols (EO content: 4-30, alkyl radical:C₁₂-C₁₈) and ethoxylated alkylphenols (EO content: 3-50, alkyl radical:C₄-C₁₂), of alkylsulfonic acids (alkyl radical: C₁₂-C₁₈) and ofalkylarylsulfonic acids (alkyl radical: C₉-C₁₈).

[0206] Suitable cationic emulsifiers are, in general, primary,secondary, tertiary or quaternary ammonium salts containing aC₆-C₁₈-alkyl, -aralkyl or heterocyclic radical, alkanolammonium salts,pyridinium salts, imidazolinium salts, oxazolinium salts, morpholiniumsalts, thiazolinium salts and salts of amine oxides, quinolinium salts,isoquinolinium salts, tropylium salts, sulfonium salts and phosphoniumsalts. Examples which may be mentioned are dodecylammonium acetate andthe corresponding hydrochloride, the chlorides or acetates of thevarious 2-(N,N,N-trimethylammonio)ethyl paraffinic acid esters,N-cetylpyridinium chloride, N-laurylpyridinium sulfate andN-cetyl-N,N,N-trimethylammonium bromide,N-dodecyl-N,N,N-trimethylammonium bromide,N,N-distearyl-N,N-dimethylammonium chloride and also the geminisurfactant N,N′-(lauryldimethyl)ethylenediamine dibromide. Numerousfurther examples may be found in H. Stache, Tensid-Taschenbuch,Carl-Hanser-Verlag, Munich, Vienna, 1981, and in McCutcheon's,Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

[0207] The components, i.e. complex in solution, optionally the solutionof the emulsifier and optionally the solution of the activator, aresubsequently introduced into the polymerization reactor.

[0208] Polymerization reactors which can be used are stirred tanks andautoclaves and also tube reactors, with the tube reactors being able tobe configured as loop reactors.

[0209] The monomer or monomers to be polymerized are mixed with thepolymerization medium. As polymerization medium, it is possible to usewater or mixtures of water with the abovementioned solvents. It shouldbe ensured that the proportion of water is at least 50% by volume, basedon the total mixture, preferably at least 90% by volume and particularlypreferably at least 95% by volume.

[0210] The solutions of the complex, of any activator used and of anyemulsifier used are combined with the mixture of monomer and aqueouspolymerization medium. The order of addition of the various componentsis not critical per se. However, it is necessary for the components tobe combined sufficiently quickly for no crystallization of any sparinglysoluble complexes formed as intermediates to occur.

[0211] The process of the present invention gives polyolefins and olefincopolymers in high yields, i.e. the activity of the complexes of thepresent invention under the conditions of emulsion polymerization isvery high.

[0212] In principle, both continuous and batchwise processes aresuitable as polymerization processes. Preference is given tosemicontinuous processes (semibatch processes) in which all componentsare mixed and further monomer or monomer mixture is metered in duringthe course of the polymerization.

[0213] The process of the present invention initially gives aqueouspolymer dispersions.

[0214] The mean particle diameter of the polymer particles in thedispersions obtained according to the present invention is from 10 to1000 nm, preferably from 50 to 500 nm and particularly preferably from70 to 350 nm. The distribution of the particle diameters can be veryuniform, but does not have to be. For some applications, in particularthose in which the solids content is high (>55%), broad or bimodaldistributions may even be preferred.

[0215] The polymers obtained by the process of the present inventionhave technically interesting properties. In the case of polyethylene,they have a high degree of crystallinity, which can be seen, forexample, from the number of branches. The number of branches found isless than 100, preferably less than 50, per 1000 carbon atoms of thepolymer as determined by ¹H-NMR and ¹³C-NMR spectroscopy.

[0216] The enthalpies of fusion of the polyethylenes obtainable by theprocess of the present invention are greater than 100 J/g, preferablygreater then 140 J/g and particularly preferably greater than 180 J/g,measured by DSC.

[0217] The molecular weight distributions of the polyethylenesobtainable by the process of the present invention are narrow, i.e. theQ values are in the range from 1.1 to 3.5, particularly preferably from1.5 to 3.1.

[0218] Advantages of the dispersions obtained according to the presentinvention are not only the low price due to the cheap monomers andprocess but also a better weathering resistance than dispersions ofpolybutadiene or butadiene copolymers. Compared to dispersions ofpolymers comprising acrylates or methacrylates as main monomer, the lowtendency to undergo hydrolysis is advantageous. Another advantage isthat most olefins are volatile and residual unpolymerized monomers caneasily be removed. A final advantage is that the polymerization does notrequire addition of molar mass regulators such as tert-dodecyl mercaptanwhich are not only difficult to separate off but also have an unpleasantodor.

[0219] The polymer particles can be obtained as such by removing thewater and, if present, the organic solvent or solvents from the aqueousdispersions obtained initially. Numerous customary methods are suitablefor removing the water and any organic solvent or solvents, for examplefiltration, spray drying or evaporation. The polymers obtained in thisway have a good morphology and a high bulk density.

[0220] The particle size can be determined by light scattering methods.An overview may be found in D. Distler “WäBrige Polymerdispersionen”,Wiley-VCH, 1st edition, 1999, chapter 4.

[0221] The dispersions obtained according to the present invention canbe used advantageously in numerous applications, for example paperapplications such as paper coating or surface sizing, also paints andvarnishes, building chemicals, adhesives raw materials, molded foams,textile and leather treatments, coatings on the reverse side of carpets,mattresses or pharmaceutical applications.

[0222] The following examples illustrate the invention.

[0223] General preliminary remarks:

[0224] All work was, unless indicated otherwise, carried out withexclusion of air and moisture using standard Schlenk techniques.Apparatus and chemicals were prepared appropriately. The polymerviscosity was determined in accordance with ISO 1628-3.

1. PREPARATION OF THE PROTONATED LIGANDS II 1.1. Preparation of theProtonated Ligand II.1

[0225] The synthesis of the protonated ligands is illustrated, by way ofexample, by the description of the synthesis of II.1.

[0226] a) 1.9 g of N-(2,6-diisopropylphenyl)benzamide (6.7 mmol) wereplaced in a dry Schlenk tube which had been flushed with argon. Afteraddition of 10 ml of thionyl chloride, the reaction solution wasrefluxed for 60 minutes. Excess SOCl₂ was taken off in a high vacuum andthe yellow oil which remained was dissolved in 20 ml of methylenechloride (absolute).

[0227] b) N-Methylhydroxylamine hydrochloride IV.1 (0.56 g, 6.7 mmol)was placed in a Schlenk tube which had been baked out and flushed withargon and was dissolved in absolute ethanol (50 ml). After addition of10 ml of triethylamine (72 mmol), the suspension formed was cooled to−40° C.

[0228] The imide chloride III.1 which had been prepared and dissolved inmethylene chloride under a) was slowly added from a dropping funnel tothe solution b) at −40° C. over a period of 30 minutes. After warming toroom temperature, the reaction mixture (yellow suspension) was stirredfor 1 hour. Subsequent thin layer chromatography (diethyl ether) of thereaction mixture indicated complete conversion.

[0229] The reaction mixture was poured into water (about 100 ml), andthe product was extracted 3× with 50 ml each time of diethyl ether. Theorganic phase was dried over Na₂SO₄, and the desiccant was filtered off.After the solvent had been distilled off on a rotary evaporator, thesemicrystalline solid formed was dissolved in small amounts of methylenechloride and filtered through silica gel. The nonpolar component, whichwas very readily soluble in ether, was completely separated off in thisway, and the polar component was enriched on the silica gel. The polartarget product was eluted by means of about 200 ml of ethanol in a waterpump vacuum.

[0230] The solvent was subsequently distilled off on a rotaryevaporator, then in a high vacuum. The resulting whitish beige solidgave, as a solution in ethanol, a deep violet color with FeCl₃: anindication of the presence of a hydroxamic acid derivative. II.1 couldbe obtained in high purity by solid phase extraction (stationary phase:silica gel 60 from Merck KGaA; eluant 1: diethyl ether for the elutionof impurities, eluant 2: ethanol for the elution of II.1).

[0231] Yield: 0.83 g (40%), empirical formula: C₂₀H₂₆N₂O, color: whitishbeige 1H-NMR (CDCl₃): 0.96 (6H, d, CH(CH ₃)₂, J=6.6 Hz), 1.09 (6H, d,CH—(CH ₃)₂, J=6.2 Hz), 3.18 (2H, sept, 2×CH(CH₃)₂), 3.47 (3H, s, N—CH₃),6.95 (2H, pseudo-d, phenyl), 7.01-7.12 (3H, m, phenyl), 7.17-7.25 (3H,m, phenyl) 13C-NMR (CDCl₃): 21.9, 25.4 (CH(CH₃)₂), 28.2 (CH(CH₃)₂), 43.7(N—CH₃), 123.2, 127.3, 127.8, 128.2, 128.9, 130.1 (C-phenyl), 131.9(quaternary C, phenyl), 146.2 (C═N—C, quaternary C, phenyl), 149.1 (C═N)IR (KBr, cm⁻¹): 3056 (w), 2962 (m), 2869 (m), 1630 (vs), 1586 (m) 1505(m), 1470 (s), 1445 (m), 1432 (m), 1383 (m), 1324 (m), 1225 (m), 1187(s), 1162 (m), 1105 (s), 1077 (w), 1044 (m), 971 (m) 917 (w), 807 (s),780 (s), 758 (s), 700 (s) MS (FAB): [M+H]⁺ (FAB)=311.2 m/z

1.2. Preparation of the Protonated Ligand II.2

[0232] Example 1.1 was repeated using the acid amide III.2

[0233] Yield: 1.63 g (63%), empirical formula: C₁₆H₁₈N₂O, color: white1H-NMR (CDCl₃): 2.16 (6H, s, 2×CH₃), 3.47 (3H, s, N—CH₃), 6.82-6.92 (3H,m, phenyl), 7.08-7.27 (5H, m, phenyl) 13C-NMR (CDCl₃): 18.6 (CH₃), 43.6(N—CH₃), 126.6, 127.7, 128.0, 128.2, 128.5 (C-phenyl), 130.1, 135.4,135.5 (quaternary C, phenyl), 149.0 (C═N) IR (KBr, cm⁻¹): 1627 (vs),1590 (m), 1578 (m), 1505 (m), 1472 (m), 1445 (m), 1426 (m), 1341 (m),1258 (m), 1237 (s), 1179 (s), 1158 (m), 1106 (m), 1092 (m), 1079 (w),1048 (m), 1025 (m), 957 (vs), 783 (vs), 774 (vs), 762 (vs), 754 (vs),726 (s), 700 (vs) MS (EI): M⁺=254.2 m/z

1.3. Preparation of the Protonated Ligand II.3

[0234] Example 1.1 was repeated using the amide III.2

[0235] Yield: 1.39 g (48%), empirical formula: C₂₀H₁₈N₂O, color: whitishbeige 1H-NMR (CDCl₃): 3.38 (3H, s, N—CH₃), 6.48-6.51 (1H, m, phenyl),6.89-7.02 (4H, m, phenyl), 7.11-7.14 (1H, m, phenyl), 7.25-7.42 (8H, m,phenyl) 13C-NMR (CDCl₃): 43.5 (N—CH₃), 122.5, 124.0, 127.4, 127.5,127.9, 128.7, 128.9, 129.0, 130.1, 130.7 (C-phenyl, C-biphenyl), 134.7,135.5 (quaternary C, phenyl), 138.4 (C═N—C, quaternary C, biphenyl),146.8 (C═N) IR (KBr, cm⁻¹): 3257 (w), 2946 (w), 1607 (s), 1580 (m), 1509(s), 1488 (s), 1447 (m), 1436 (s), 1422 (s), 1393 (m), 1387 (m), 1243(s), 1196 (s), 1073 (m), 963 (s), 783 (m), 770 (vs), 756 (vs), 743 (vs),698 (vs) MS (EI): M⁺=302.2 m/z

Example 1.4 Synthesis of the Protonated Ligand II.4

[0236] Example 1.1. was repeated using the amide III.4

[0237] Yield: 1.03 g (42%), empirical formula: C₁₄H₁₄N₂O, color: whitishbeige 1H-NMR (CDCl₃): 3.47 (3H, s, N—CH₃), 6.56 (2H, d, phenyl), 6.87(1H, pseudo-t, phenyl), 7.01 (2H, pseudo-t, phenyl), 7.25 (2H, pseudo-d,phenyl), 7.24-7.43 (3H, m, phenyl) 13C-NMR (CDCl₃): 43.4 (N—CH₃), 121.0,123.3, 127.8, 128.6, 129.0, 129.1, 130.4 (C-phenyl), 138.1 (C═N—C,quaternary C, phenyl), 146.7 (C═N, quaternary C) IR (KBr, cm⁻¹): 3049(w), 2943 (w), 1615 (vs), 1603 (s), 1574 (m), 1509 (s), 1482 (m), 1447(m), 1428 (m), 1196 (s), 1160 (m), 1071 (w), 971 (s), 758 (s), 726 (s),697 (vs) MS (EI): M⁺=226.1 m/z

Example 1.5

[0238] Example 1.1. was repeated using N-isopropylhydroxylaminehydrochloride IV.5

[0239] Yield: 0.63 g (36%), empirical formula: C₂₂H₃₀N₂O, color: lightyellow m.p.: 94-96° C.

[0240] 1H-NMR (CDCl₃): 0.98 (6H, d, Ph—CH—(CH ₃)₂, J=6.2 Hz), 1.11 (6H,d, Ph—CH—(CH ₃)₂, J=6.2 Hz), 1.37 (6H, d, N—CH—(CH ₃)₂, J=6.6 Hz), 3.16(2H, sept, 2×Ph—CH—(CH₃)₂), 4.03 (1H, sept, N—CH—(CH₃)₂, J=6.6 Hz), 6.95(2H, pseudo-d, phenyl), 7.02-7.12 (3H, m, phenyl), 7.20-7.27 (3H, m,phenyl) 13C-NMR (CDCl₃): 20.0, 21.9, 25.4, 28.2 (CH(CH₃)₂, CH(CH₃)₂),54.8 (N—CH₃), 123.0, 127.5, 127.7, 128.3, 128.5, 129.9 (C-phenyl), 132.5(quaternary C, phenyl), 145.9 (C═N—C, quaternary C, phenyl), 148.1 (C═N)IR (KBr, cm⁻¹): 3433 (w), 3064 (w), 3006 (w), 2968 (s), 2948 (m), 2931(m), 2867 (m), 1683 (w), 1598 (vs), 1503 (s), 1461 (s), 1436 (m), 1385(m), 1378 (m), 1360 (s), 1343 (w), 1335 (w), 1320 (w), 1256 (w), 1173(vs), 1123 (w), 1104 (w), 1067 (vs), 1040 (w), 978 (m), 930 (w), 924(w), 822 (w), 808 (s), 781 (m), 760 (s), 702 (s) MS (EI): M⁺=338.3 m/z

Example 1.6 Preparation of the Protonated Ligand II.6

[0241] Example 1.1. was repeated using N-para-tolylhydroxylamine

[0242] The preparation of IV.6 was carried out as follows:

[0243] 0.7 g of p-NO₂-toluene (5.1 mmol) was placed in a 50 mlround-bottomed flask and partly dissolved in 6 ml of methanol. Afteraddition of NH₄Cl (0.27 g, 5.0 mmol) dissolved in 2 ml of water, theresulting suspension was heated under reflux as described in LiebigsAnn. Chem. 1985, 4, 673. Zinc powder was added in portions of 400 mg(2×) and 600 mg (2×) in the order indicated. After the 4th addition(total of 2 g, 31 mmol) and refluxing for 1 hour, thin layerchromatography indicated that there was no longer any starting materialpresent.

[0244] The contents of the reaction flask were poured into a glassbeaker filled with water. Excess zinc was filtered off, and the filtratewas transferred to a separating funnel and extracted 3× with 25 ml eachtime of methylene chloride. The combined organic phases were dried overNa₂SO₄. After taking off the solvent on a rotary evaporator, theresulting yellow solid was dried in a high vacuum.

[0245] Yield: 0.53 g (4.3 mmol)

[0246] The product was subsequently worked up by a method analogous tothat in the preparation of II.1.

[0247] Yield: 0.30 g (18%), empirical formula: C₂₆H₃₀N₂O, color: brown1H-NMR (CDCl₃): 0.90 (6H, d, CH(CH ₃)₂, J=7.0 Hz), 1.11 (6H, d, CH(CH₃)₂, J=7.0 Hz), 2.19 (3H, s, N—Ph—CH₃), 3.17 (2H, sept, 2×CH(CH₃)₂,J=7.0 Hz), 6.82-6.91 (4H, m, phenyl), 6.96-7.23 (8H, m, phenyl) 13C-NMR(CDCl₃): 14.0, 20.9, 22.0, 22.5, 25.2, 28.4, 31.5 (5×CH₃, 2×CH), 123.4,125.4, 127.4, 127.8, 127.9, 129.0, 129.6, 129.7 (C-phenyl), 132.1, 137.4(quaternary C, phenyl), 141.0 (N—C, quaternary C, phenyl), 145.4 (C═N—C,quaternary C, phenyl), 150.5 (C═N) IR (KBr, cm⁻¹): 2964 (s), 2927 (m),2867 (m), 1600 (vs), 1571 (s) 1507 (s), 1461 (s), 1322 (m), 1302 (w),1285 (w), 1260 (m), 1239 (m), 1187 (w), 1106 (m), 1077 (w), 1044 (m),818 (s), 787 (s), 776 (s), 758 (s), 697 (s) MS (FAB): [M⁺H]⁺=387.3 m/z

Example 1.7 Preparation of the Protonated Ligand II.7

[0248]

[0249] In the preparation of II.7, N,N′-dimethylhydrazine served asreagent and as base. No triethylamine was added. The procedure wasmodified as follows:

[0250] N,N′-Dimethylhydrazine (0.58 ml, 0.46 g, 7.7 mmol) was placed ina Schlenk tube which had been baked out and flushed with argon and wasdissolved in absolute ethanol (50 ml).

[0251] Imide chloride III.1 (10 ml, 1.08 g, 3.6 mmol, c=0.115 g/ml)dissolved in methylene chloride was slowly added from a dropping funnelat −45° C. over a period of 60 minutes. After warming to roomtemperature, the reaction mixture was stirred for 1 hour (color change:colorless→yellow). The hydrazinium salt formed in the reactionprecipitated, resulting in a turbid suspension. Thin layerchromatography (diethyl ether/hexane=1/1) subsequently indicatedcomplete conversion.

[0252] The reaction mixture was poured into water (about 100 ml), andthe product wass extracted 3× with 50 ml each time of diethyl ether. Thecombined organic phases were dried over Na₂SO₄, and the desiccant wasfiltered off. After taking off the solvent on a rotary evaporator, theresulting viscous oil was dried in a high vacuum.

[0253] Yield: 1.10 g (94%), empirical formula: C₂₁H₂₉N₂O, color: brown1H-NMR (CDCl₃): 0.94 (6H, d, CH(CH ₃)₂, J=7.0 Hz), 1.06 (6H, d,CH(CH₃)₂, J=6.6 Hz), 2.64 (3H, s, CH ₃—NH), 2.90 (3H, s, N—CH₃) 2.94(2H, sept, 2×CH(CH₃)₂), 6.78-6.86 (3H, m, phenyl), 7.01-7.14 (5H, m,phenyl) 13C NMR (CDCl₃): 21.8, 24.1 (CH (CH₃)₂), 28.1 (CH(CH₃)₂), 36.4(NH—CH₃), 39.2 (N—CH₃), 122.1, 122.2, 127.8, 128.1, 128.8, 133.1, 138.2(C-phenyl), 144.7 (C═N—C, quaternary C, phenyl), 157.3 (C═N) IR (KBr,cm⁻¹): 3244 (w), 3062 (w), 3022 (w), 2973 (m), 2960 (m), 1609 (vs), 1596(s), 1586 (vs), 1576 (s), 1492 (w), 1439 (m), 1382 (m), 1364 (s), 1329(m), 1262 (m), 1183 (w), 1111 (m), 1069 (s), 1046 (m), 1025 (s), 924(m), 845 (s), 824 (m), 808 (w), 799 (m), 772 (vs), 760 (vs), 714 (vs),700 (vs) MS (EI): M⁺=323.3 m/z TABLE 1 Overview of protonated ligands ofthe formula II Prot. ligand R¹ R² R³ Nu II.1 2,6-(i-C₃H₇)₂C₆H₃ C₆H₅ CH₃O II.2 2,6-(CH₃)₂C₆H₃ C₆H₅ CH₃ O II.3 2-(C₆H₅)—C₆H₄ C₆H₅ CH₃ O II.4 C₆H₅C₆H₅ CH₃ O II.5 2,6-(i-C₃H₇)₂C₆H₃ p-CH₃—C₆H₄ i-C₃H₇ O II.62,6-(i-C₃H₇)₂C₆H₃ p-CH₃—C₆H₄ CH₃ O II.7 2,6-(i-C₃H₇)₂C₆H₃ C₆H₅ CH₃ N—CH₃

2.1. Syntheses of Complexes of the Formula Ia

[0254] II.1 (0.28 g, 0.90 mmol) was placed in a baked out Schlenk tubewhich had been flushed with argon, and dissolved in 20 ml of THF(absolute), deprotonated at −80° C. in a cold bath (EtOH, N₂) by meansof n-buthyllithium (0.45 ml, 0.90 mmol, 2.0 M in pentane) (color change:orange→dark red) and stirred at the temperature indicated for 1 hour.

[0255] After addition of the transition metal halide (ZrCl₄, 0.21 g,0.90 mmol) at −80° C., the cold bath was removed and the solution wassubsequently stirred overnight.

[0256] The THF was taken off in a high vacuum and the orange-brownresidue was suspended in 50 ml of methylene chloride (absolute). TheLiCl formed in the reaction was filtered off from the suspension. Thesolution was subsequently evaporated to dryness in a high vacuum, theresidue was digested once with 10 ml of hexane (absolute) and washed.The solvent was syphoned off, and the pulverulent orange complex I.a.1was dried in a high vacuum.

[0257] Yield: 0.41 g (90%), empirical formula: C₂₀H₂₅Cl₃N₂OZr, color:orange 1H-NMR (CD₂Cl₂): 1.04 (6H, d, CH(CH ₃)₂), 1.32 (6H, d, CH(CH₃)₂), 1.81 (CH₂, broad, coordinated THF), 3.33 (5H, m, N—CH₃,2×CH(CH₃)₂, signals superimposed), 3.83 (CH₂—O, broad, coordinated THF),6.94-7.02 (3H, m, phenyl), 7.10-7.35 (5H, m, phenyl) 13C-NMR (CD₂Cl₂):24.2, 25.9 (CH(CH₃)₂), 28.1 (CH(CH₃)₂), 41.6 (N—CH₃), 123.6, 124.2,126.1, 128.5, 128.7, 129.1, 129.3, 129.4, 130.6, 143.9, 144.2(C-phenyl), 161.7 (C═N).

[0258] In an analogous way, the complex Ia.2 was obtained by reaction ofdeprotonated II.2 with ZrCl₄.

[0259] Yield: 0.82 g (86%), empirical formula: C₁₆H₁₇Cl₃N₂OZr, color:orange 1H-NMR (CD₂Cl₂): 1.91 (CH₂, broad, coordinated THF), 2.28, 2.31,2.34, 2.39 (6H, 4×s, Ph—CH ₃, isomers), 3.27, 3.33 (3H, 2×s, N—CH ₃,isomers), 3.85 (CH₂—O, broad, coordinated THF), 4,53 (CH₂—O, broad,coordinated THF), 6.83-7.37 (8H, m, phenyl) 13C-NMR (CD₂Cl₂): 18.7,19.5, 19.7, 20.7, 20.9 (Ph—CH₃, isomers), 25.8 (CH₂, THF), 39.5, 41.3,41.9, 42.2 (N—CH₃, isomers), 69.3 (CH₂—O, THF), 125.5, 126.0, 127.2,127.9, 128.0, 128.1, 128.4, 128.7, 128.9, 129.2, 130.1, 130.3, 130.4,130.5, 130.9, 131.4, 133.1, 133.4, 133.8, 134.4, 134.7, 146.3 (phenyl,isomers), 161.3 (C═N).

[0260] In an analogous way, the complex Ia.3 was obtained by reaction ofthe protonated II.3 with ZrCl₄.

[0261] Yield: 0.71 g (88%), empirical formula: C₂₀H₁₇Cl₃N₂OZr, color:brown 1H-NMR (CD₂Cl₂): 1.88 (4H, 2×CH₂, broad, coordinated THF), 2.00(CH₂, coordinated THF, shoulder), 2.33, 2.84, 2.97, 3.15 (3H, s, N—CH₃,plurality of singlets which add up to a total of 3 H, isomers, signal at2.84 has the highest intensity), 3.82 (4H, 2×CH₂—O, broad, coordinatedTHF), 4.56 (CH₂—O, broad, coordinated THF), 6.90-7.43 (14H, m, phenyl)13C-NMR (CD₂Cl₂): 25.9 (CH₂, THF), 41.1 (N—CH₃), 69.2 (CH₂—O, THF),126.3, 127.2, 127.8, 127.9, 128.1, 128.5, 128.6, 128.7, 129.3, 129.4,129.7, 130.2, 130.3 (C-phenyl), 131.2, 139.9 (quaternary C, phenyl),144.5 (C═N—C, quaternary C, phenyl),160.9 (C═N).

[0262] In an analogous way, the complex Ia.4 was obtained by reaction ofdeprotonated II.4 with ZrCl₄.

[0263] Yield: 0.58 g (92%), empirical formula: C₁₄H₁₃Cl₃N₂OZr, color:yellow 1H-NMR (CD₂Cl₂): 1.86 (4H, 2×CH₂, coordinated THF), 2.78, 3.32(3H, 2×s, N—CH₃, isomers, signal at 2.78 has the highest intensity),3.84 (4H, broad, 2×CH₂—O, coordinated THF), 4.54 (CH₂—O, coordinatedTHF), 6.92-7.35 (10H, m, phenyl) 13C-NMR (CD₂Cl₂): 25.8 (CH₂, THF), 40.0(N—CH₃), 125.2, 126.5, 128.3. 128.4, 128.6, 128.8, 129.0, 129.1, 129.2,130.8 (C-phenyl), 146.3 (C═N—C, quaternary C, phenyl), 159.3 (C═N).

[0264] In an analogous way, the complex Ia.5 was obtained by reaction ofdeprotonated II.5 with ZrCl₄.

[0265] Yield: 0.28 g (64%), empirical formula: C₂₂H₂₉Cl₃N₂OZr, color:white 1H-NMR (CD₂Cl₂): 1.00-1.45 (15H, m, 2×Ph—CH(CH ₃)₂, N—CH(CH ₃),1.61 (3H, d, N—CH(CH ₃), J=6.6 Hz), 1.83 (CH₂, broad, coordinated THF),2.10 (CH₂, broad, coordinated THF), 3.28-4.02 (3H, m, 3×CH(CH₃)₂,superimposed septets), 3.76 (CH₂—O, broad, coordinated THF), 4.70(CH₂—O, broad, coordinated THF), 6.92-7.15 (2H, m, phenyl), 7.18-7.46(6H, m, phenyl) 13C-NMR (CD₂Cl₂): 20.0, 20.1, 22.0, 23.8, 24.3, 25.9,26.1, 26.3, 28.2, 29.0, 29.2 (CH(CH₃)₂, CH(CH₃)₂, isomers), 55.1 (N—CH),123.5, 123.6, 123.8, 124.1, 126.1, 126.3, 127.9, 128.5, 128.6, 128.8,129.0, 129.2, 129.6, 129.7, 130.5, 131.9, 143.8, 144.5, 146.9, 147.4,155.0 (phenyl, isomers), 162.0 (C═N).

[0266] In an analogous way, the complex Ia.6 was obtained by reaction ofdeprotonated II.6 with ZrCl₄.

[0267] Yield: 0.29 g (90%), empirical formula: C₂₆H₂₉Cl₃N₂OZr, color:beige 1H-NMR (CD₂Cl₂): 1.05-1.35 (12H, m, 2×CH(CH ₃)₂), 1.82 (CH₂,broad, coordinated THF), 1.97 (CH₂, coordinated THF, shoulder), 2.27(3H, s, N—Ph—CH ₃), 3.20, 3.40 (2H, 2×sept, CH(CH₃)₂), 3.77 (CH₂—O,broad, not coordinated THF), 4.48 (CH₂—O, coordinated THF), 6.77-7.67(12H, m, phenyl).

[0268] In an analogous way, the complex Ia.7 was obtained by reaction ofdeprotonated II.7 with ZrCl₄.

[0269] Yield: 0.,71 g (85%), empirical formula: C₂₁H₂₈Cl₃N₃Zr, color:yellow 1H-NMR (CD₂Cl₂): 0.93-1.24 (12H, 4×d, 2×CH(CH ₃)₂), 1.82 (CH₂,broad, coordinated THF), 2.94, 3.07, 3.18, 3.29 (5H, 4×s, sept, N—CH₃,2×CH(CH₃)₂, isomers, signal at 3.18 has the highest intensity), 3.39,3.48, 3.57, 3.89 (3H, 3×s, N—CH₃, isomers), 3.84 (CH₂—O, coordinatedTHF), 4.56 (CH₂—O, coordinated THF), 6.90-7.60 (8H, m, phenyl) 13C-NMR(CD₂Cl₂): 21.8, 22.6, 24.2, 25.3, 25.9, 27.0, 28.2, 29.2 (CH(CH₃)₂,CH(CH₃)₂, isomers), 34.9, 38.8, 40.4 (N—CH₃, isomers), 123.0, 124.0,124.3, 128.3, 128.6, 128.9, 129.5, 129.7, 129.8, 133.0 (C-phenyl, 2isomers), 143.8, 144.0 (C═N—C, quaternary C, phenyl, 2 isomers), 146.1(C═N).

[0270] In an analogous way, the complex Ia.8 was obtained by reaction ofdeprotonated II.2 with TiCl₄.

[0271] Yield: 0.67 g (95%), empirical formula: C₁₆H₁₇Cl₃N₂OTi, color:orange 1H-NMR (CD₂Cl₂): 2.13 (3H, s, Ph—CH ₃), 2.34 (3H, s, Ph—CH ₃),3.40, 3.49, 3.63 (3H, s, N—CH₃, 3 singlets of decreasing intensity,total of 3H, isomers, signal at 3.40 ppm has the highest intensity),6.85 (3H, pseudo-d, phenyl), 7.12-7.41 (5H, m, phenyl) 13C-NMR (CD₂Cl₂):19.6, 20.4 (Ph—CH₃), 30.0, 39.2, 41.5 (N—CH₃, isomers), 125.8, 126.0,128.1, 128.5, 128.7, 129.0, 129.3, 131.0 (C-phenyl), 131.7, 133.2, 133.5(quaternary C, phenyl, isomers), 145.4, 149.9 (C═N—C, quaternary C,phenyl, isomers), 160.3 (C═N)

[0272] In an analogous way, the complex Ia.9 was obtained by reaction ofdeprotonated II.2 with VCl₄.

[0273] Yield: 0.58 g (91%), empirical formula: C₁₆H₁₇Cl₃N₂OV, color:dark green 1H-NMR: The complex is paramagnetic and no signals could beassigned.

[0274] In an analogous way, the complex Ia.10 was obtained by reactionof deprotonated II.7 with TiCl₄.

[0275] Yield: 0.56 g (95%), empirical formula: C₂₁H₂₈Cl₃N₃Ti, color:bluish green 1H-NMR (CD₂Cl₂): 1.05 (6H, d, CH(CH ₃)₂, J=6.9 Hz), 1.34(6H, d, CH(CH ₃)₂, J=6.6 Hz), 2.93 (2H, sept, 2×CH(CH₃)₂), 3.38 (3H, s,N—CH₃), 4.38 (3H, s, Ti—N—CH ₃), 6.99 (2H, pseudo-d, phenyl), 7.07-7.15(3H, m, phenyl), 7.27-7.36 (3H, m, phenyl) 13C-NMR (CD₂Cl₂): 23.9, 25.3(CH(CH₃)₂), 28.6 (CH(CH₃)₂), 38.0 (N—CH₃), 45.2 (Ti—N—CH₃), 123.8,128.0, 128.7, 128.9, 129.0, 131.4, 141.2 (C-phenyl), 150.9, (C═N—C,quaternary C, phenyl), 160.0 (C═N). TABLE 2 Overview of novel complexesof the formula I a Compound R¹ R² R³ Nu M I a.1 2,6-(i-C₃H₇)₂C₆H₃ C₆H₅CH₃ O Zr I a.2 2,6-(CH₃)₂C₆H₃ C₆H₅ CH₃ O Zr I a.3 2-(C6H5)-C6H4 C₆H₅ CH₃O Zr I a.4 C₆H₅ C₆H₅ CH₃ O Zr I a.5 2,6-(i-C₃H₇)₂C₆H₃ p-CH₃—C₆H₄ i-C₃H₇O Zr I a.6 2,6-(i-C₃H₇)₂C₆H₃ p-CH₃—C₆H₄ CH₃ O Zr I a.7 2,6-(i-C₃H₇)₂C₆H₃C₆H₅ CH₃ N—CH₃ Zr I a.6 2,6-(CH₃)₂C₆H₃ C₆H₅ CH₃ O Ti I a.92,6-(CH₃)₂C₆H₃ C₆H₅ CH₃ O V I a.10 2,6-(i-C₃H₇)₂C₆H₃ C₆H₅ CH₃ N—CH₃ Tii-C₃H₇: isopropyl; p-CH₃—C₆H₄: para-tolyl I b.1

2.2. Synthesis of Complexes of the Formula Ib

[0276] General procedure described by way of example for Ib.1 II.1 (0.65g, 2.08 mmol) was placed in a baked-out Schlenk tube which had beenflushed with argon and was dissolved in 20 ml of THF (absolute) to forma pink solution which was deprotonated at −110° C. in a cold bath (EtOH,N₂) by means of n-BuLi (1.2 ml, 2.4 mmol, 2.0 M in pentane) (colorchange: pink→yellow)

[0277] After addition of the transition metal halide (ZrCl₄, 0.21 g,0.90 mmol, <1/2 meq) at −110° C., the mixture was stirred at thistemperature for 1 hour. The cold bath was removed. After warming to roomtemperature, the mixture was stirred overnight, resulting in a clear,yellow solution.

[0278] The THF was taken off in a high vacuum and the residue wassuspended in 50 ml of methylene chloride (absolute). The fine LiClformed in the reaction was removed from the suspension by filtration (G4frit and Celite®). The filtrate was subsequently evaporated to drynessin a high vacuum, and the residue was digested once with 10 ml of hexane(absolute) and washed. The solvent was syphoned off and the pulverulentyellow complex I.b.1 was dried in a high vacuum.

[0279] Yield: 0.54 g (77%), empirical formula: C₄₀H₅₀Cl₂N₄O₂Zr, color:whitish beige 1H-NMR (CD₂Cl₂): 0.23, 0.43, 0.92, 1.04 (24H, 4×d, 4×CH(CH₃)₂), 4×J=6.6 Hz), 2.89 (2H, sept, 2×CH(CH₃)₂), 3.18 (2H, sept,2×CH(CH₃)₂), 3.40, 3.54, 3.60, 3.97 (6H, 4×s, N—CH₃, isomers, signal at3.60 has the highest intensity), 6.80-7.29 (16H, m, phenyl) 13C-NMR(CD₂Cl₂): 24.5, 25.1, 25.9, 26.2, 27.9, 28.1 (CH(CH ₃)₂, CH(CH ₃)₂),43.6 (N—CH₃), 123.5, 124.2, 124.8, 125.8, 127.7, 127.9, 128.3, 128.7,129.0, 129.4, 130.0, 130.3 (C-phenyl), 143.3, 143.5, 145.5 (C═N—C,quaternary C, phenyl), 159.8 (C═N).

3. Polymerization Experiments 3.1. Polymerization in an Autoclave

[0280] The indicated amount of the complex to be studied, 2 ml of 30%strength by weight MAO solution in toluene (commercially available fromWitco) and 400 ml of toluene were placed in a 1 l steel autoclave whichhad been made inert. The autoclave was pressurized with ethylene to apressure of 40 bar at 70° C. This pressure was kept constant over thepolymerization time of 90 minutes by introduction of further ethylene.The reaction was stopped by venting and the polymer was isolated byfiltration, subsequent washing with methanol and drying under reducedpressure. TABLE 3 Polymerization results Ethylene polymerization (40bar) Amount of Activity Yield η Time complex used Complex[gmmol⁻¹h⁻¹bar⁻¹] [g] [dl/g] [min] [mg] I a.1 50.2 9.5  9.51 30 4.8 Ia.2 45.1 12.0 14.01 30 6 I a.3 68.4 4.8 11.41 35 1.5 I a.4 78.7 6.724.95 60 0.9 I a.5 88.4 11.9  4.43 90 1.2 I a.6 51.3 8.8  8.76 75 2 Ia.7 76.8 6.2 15.6  45 1.4 I a.8 18.8 7.4 54.33 60 4 I a.9 5.3 6.2 19.1890 8 I a.10 28 1.0 Not 15 1.7 deter- mined I b.1 30.6 9.4 41.38 90 4

3.2 Copolymerization of Ethylene and Hexene

[0281] The procedure described under 3.1 was repeated, but 12.5 or 25 mlof 1-hexene were introduced into the autoclave at the beginning togetherwith the other reagents. TABLE 4 Copolymerization resultsCopolymerization (ethene/hexene, 40 bar) Amount of Amount 1-hexeneActivity Of compex added [gmmol⁻¹h⁻¹ Yield η Time used Complex [ml]bar⁻¹] [g] [dl/g] [min] [mg] I a.4 12.5 131.1 12.4 11.40 60 1.0 I a.4 2539.2 5.1 4.63 75 1.1 I a.8 12.5 13.2 7.0 9.94 85 3.8 I a.8 25 8.7 1.77.53 30 4.0

We claim:
 1. A complex of the formula Ia or Ib,

where the variables are defined as follows: Nu is selected from among O,S, N—R⁴, P—R⁴, M is selected from among Ti, Zr, Hf, V, Nb, Ta, Cr, Ni,Pd; h is an integer from 0 to 4; y corresponds to the oxidation state ofM minus 1; z corresponds to the oxidation state of M minus 2; X areidentical or different and are selected from among halogen,C₁-C₆-alkoxy, acetylacetonate, N(R⁵R⁶ ), C₁-C₈-alkyl, C₃-C₁₂-cycloalkyl,C₇-C₁₃-aralkyl and C₆-C₁₄-aryl, R¹, R⁴ are identical or different andare selected from among hydrogen, C₁-C₁₈-alkyl, substituted orunsubstituted, C₂-C₁₈-alkenyl, substituted or unsubstituted, having from1 to 4 isolated or conjugated double bonds; C₃-C₁₂-cycloalkyl,substituted or unsubstituted, C₇-C₁₃-aralkyl, C₆-C₁₄-aryl, unsubstitutedor substituted by one or more identical or different substituentsselected from among C₁-C₁₈-alkyl, substituted or unsubstituted,C₂-C₁₈-alkenyl, substituted or unsubstituted, C₃-C₁₂-cycloalkyl,C₇-C₁₃-aralkyl, C₆-C₁₄-aryl, halogen, C₁-C₆-alkoxy, substituted orunsubstituted, C₆-C₁₄-aryloxy, SiR⁵R⁶R⁷ and O—SiR⁵R⁶R⁷; five- tosix-membered nitrogen-containing heteroaryl radicals, unsubstituted orsubstituted by one or more identical or different substituents selectedfrom among C₁-C₁₈-alkyl, substituted or unsubstituted, C₂-C₁₈-alkenyl,substituted or unsubstituted, C₃-C₁₂-cycloalkyl, C₇-C₁₃-aralkyl,C₆-C₁₄-aryl, halogen, C₁-C₆-alkoxy, C₆-C₁₄-aryloxy, SiR⁵R⁶R⁷ andO—SiR⁵R⁶R⁷; R² is C₆-C₁₄-aryl, unsubstituted or substituted by one ormore identical or different substituents, or a five- to six-memberednitrogen-containing heteroaryl radical, unsubstituted or substituted byone or more identical or different substituents, where the substituentsare as defined above; R³ is C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, substituted orunsubstituted, having from one to 4 isolated or conjugated double bonds,C₃-C₁₂-cycloalkyl, substituted or unsubstituted, C₇-C₁₃-aralkyl,C₆-C₁₄-aryl, unsubstituted or substituted by or more identical ordifferent substituents, or a five- to six-membered nitrogen-containingheteroaryl radical, unsubstituted or substituted by one or moreidentical or different substituents, where the substituents are asdefined above; where adjacent radicals R¹ to R⁴ may be joined to oneanother to form a 5- to 12-membered ring which may in turn bearsubstituents selected from among C₁-C₈-alkyl, substituted orunsubstituted, C₂-C₈-alkenyl, substituted or unsubstituted, having fromone to 4 isolated or conjugated double bonds, C₃-C₁₂-cycloalkyl,substituted or unsubstituted, C₇-C₁₃-aralkyl and C₆-C₁₄-aryl; L¹ is anuncharged organic or inorganic ligand, R⁵ to R⁷ are identical ordifferent and are selected from among hydrogen, C₁-C₈-alkyl,C₃-C₁₂-cycloalkyl, C₇-C₁₃-aralkyl and C₆-C₁₄-aryl.
 2. A complex asclaimed in claim 1, wherein Nu is oxygen, M is selected from among Tiand Zr, h is not equal to 0 and X is halogen.
 3. A complex as claimed inclaim 1, wherein M is selected from among Ni or Pd, h is not equal to 0and L¹ is selected from among phosphines (R⁸)_(x)PH_(3−x), amines(R⁸)_(x)NH_(3−x), ethers (R⁸)₂O, H₂O, alcohols (R⁸)OH, pyridine,pyridine derivatives of the formula C₅H_(5−x)(R⁸)_(x)N, CO, C₁-C₁₂-alkylnitrites, C₆-C₁₄-aryl nitrites and ethylenically unsaturated double bondsystems, where x is an integer from 0 to 3, and R⁸ are identical ordifferent and are selected from among C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl,substituted or unsubstituted, having from one to 4 isolated orconjugated double bonds, C₃-C₁₂-cycloalkyl, substituted orunsubstituted, C₇-C₁₃-aralkyl, C₆-C₁₄-aryl, unsubstituted or substitutedby one or more identical or different substituents, and five- tosix-membered nitrogen-containing heteroaryl radicals, unsubstituted orsubstituted by one or more identical or different substituents.
 4. Aprocess for the polymerization or copolymerization of olefins or ofstyrene using complexes of the formula Ia or Ib as claimed in any ofclaims 1 to
 3. 5. A process for preparing polyolefin waxes usingcomplexes of the formula Ia or Ib as claimed in any of claims 1 to 3 anda regulator, in particular hydrogen.
 6. A process for preparingcomplexes as claimed in claim 1 or 2, which comprises firstlydeprotonating a protonated ligand of the formula II

by means of a base and subsequently reacting the product with a metalcompound MX_(y+1), where M is selected from among Ti, Zr, Hf, V, Nb, Ta,Cr, Ni and Pd and X is halogen, C₁-C₆-alkoxy, acetylacetonate, N(R⁵R⁶),C₁-C₈-alkyl, C₃-C₁₂-cycloalkyl, C₇-C₁₃-aralkyl or C₆-C₁₄-aryl andMX_(y+1) may optionally be stabilized by uncharged inorganic or organicligands.
 7. A process for preparing a supported catalyst for thepolymerization or copolymerization of olefins, which comprisesdepositing one or more complexes as claimed in any of claims 1 to 3 andoptionally an activator on a solid support.
 8. A supported catalyst forthe polymerization or copolymerization of olefins which is obtainable bya process as claimed in claim
 7. 9. A process for the polymerization orcopolymerization of olefins using a supported catalyst as claimed inclaim
 8. 10. A process for the emulsion polymerization orcopolymerization of ethylene or other 1-olefins and optionally furtherolefins using a complex of the formula Ia or b as claimed in claim 1 or3.